A nanocrystalline (NC) material is a
polycrystalline
A crystallite is a small or even microscopic crystal which forms, for example, during the cooling of many materials. Crystallites are also referred to as grains.
Bacillite is a type of crystallite. It is rodlike with parallel longulites.
Stru ...
material with a
crystallite
A crystallite is a small or even microscopic crystal which forms, for example, during the cooling of many materials. Crystallites are also referred to as grains.
Bacillite is a type of crystallite. It is rodlike with parallel longulites.
Stru ...
size of only a few
nanometer
330px, Different lengths as in respect to the molecular scale.
The nanometre (international spelling as used by the International Bureau of Weights and Measures; SI symbol: nm) or nanometer (American and British English spelling differences#-re ...
s. These materials fill the gap between
amorphous
In condensed matter physics and materials science, an amorphous solid (or non-crystalline solid, glassy solid) is a solid that lacks the long-range order that is characteristic of a crystal.
Etymology
The term comes from the Greek ''a'' ("wi ...
materials without any
long range order and conventional coarse-grained materials. Definitions vary, but nanocrystalline material is commonly defined as a
crystallite
A crystallite is a small or even microscopic crystal which forms, for example, during the cooling of many materials. Crystallites are also referred to as grains.
Bacillite is a type of crystallite. It is rodlike with parallel longulites.
Stru ...
(grain) size below 100 nm. Grain sizes from 100–500 nm are typically considered "ultrafine" grains.
The grain size of a NC sample can be estimated using
x-ray diffraction
X-ray crystallography is the experimental science determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to diffract into many specific directions. By measuring the angles ...
. In materials with very small grain sizes, the diffraction peaks will be broadened. This broadening can be related to a crystallite size using the
Scherrer equation (applicable up to ~50 nm), a
Williamson-Hall plot,
or more sophisticated methods such as the Warren-Averbach method or computer modeling of the diffraction pattern. The crystallite size can be measured directly using
transmission electron microscopy
Transmission electron microscopy (TEM) is a microscopy technique in which a beam of electrons is transmitted through a specimen to form an image. The specimen is most often an ultrathin section less than 100 nm thick or a suspension on a gr ...
.
Synthesis
Nanocrystalline materials can be prepared in several ways. Methods are typically categorized based on the
phase of matter
In the physical sciences, a phase is a region of space (a thermodynamic system), throughout which all physical properties of a material are essentially uniform. Examples of physical properties include density, index of refraction, magnetizat ...
the material transitions through before forming the nanocrystalline final product.
Solid-state processing
Solid-state processes do not involve melting or evaporating the material and are typically done at relatively low temperatures. Examples of solid state processes include
mechanical alloying Mechanical alloying (MA) is a solid-state and powder processing technique involving repeated cold welding, fracturing, and re-welding of blended powder particles in a high-energy ball mill to produce a homogeneous material. Originally developed to ...
using a high-energy ball mill and certain types of
severe plastic deformation processes.
Liquid processing
Nanocrystalline metals can be produced by rapid
solidification
Freezing is a phase transition where a liquid turns into a solid when its temperature is lowered below its freezing point. In accordance with the internationally established definition, freezing means the solidification phase change of a liquid o ...
from the liquid using a process such as
melt spinning. This often produces an amorphous metal, which can be transformed into an nanocrystalline metal by
annealing above the
crystallization temperature.
Vapor-phase processing
Thin film
A thin film is a layer of material ranging from fractions of a nanometer (monolayer) to several micrometers in thickness. The controlled synthesis of materials as thin films (a process referred to as deposition) is a fundamental step in many a ...
s of nanocrystalline materials can be produced using
vapor deposition
Vacuum deposition is a group of processes used to deposit layers of material atom-by-atom or molecule-by-molecule on a solid surface. These processes operate at pressures well below atmospheric pressure (i.e., vacuum). The deposited layers can r ...
processes such as
MOCVD
Metalorganic vapour-phase epitaxy (MOVPE), also known as organometallic vapour-phase epitaxy (OMVPE) or metalorganic chemical vapour deposition (MOCVD), is a chemical vapour deposition method used to produce single- or polycrystalline thin films. ...
.
Solution processing
Some metals, particularly
nickel
Nickel is a chemical element with symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive but large pieces are slow to ...
and
nickel alloys, can be made into nanocrystalline foils using
electrodeposition.
Mechanical properties
Nanocrystalline materials show exceptional mechanical properties relative to their coarse-grained varieties. Because the volume fraction of grain boundaries in nanocrystalline materials can be as large as 30%,
the mechanical properties of nanocrystalline materials are significantly influenced by this amorphous grain boundary phase. For example, the elastic modulus has been shown to decrease by 30% for nanocrystalline metals and more than 50% for nanocrystalline ionic materials.
This is because the amorphous grain boundary regions are less dense than the crystalline grains, and thus have a larger volume per atom,
. Assuming the interatomic potential,
, is the same within the grain boundaries as in the bulk grains, the elastic modulus,
, will be smaller in the grain boundary regions than in the bulk grains. Thus, via the
rule of mixtures
In materials science, a general rule of mixtures is a weighted mean used to predict various properties of a composite material . It provides a theoretical upper- and lower-bound on properties such as the elastic modulus, mass density, ultimate te ...
, a nanocrystalline material will have a lower elastic modulus than its bulk crystalline form.
Nanocrystalline metals
The exceptional yield strength of nanocrystalline metals is due to
grain boundary strengthening
In materials science, grain-boundary strengthening (or Hall–Petch strengthening) is a method of strengthening materials by changing their average crystallite (grain) size. It is based on the observation that grain boundaries are insurmounta ...
, as grain boundaries are extremely effective at blocking the motion of dislocations. Yielding occurs when the stress due to dislocation pileup at a grain boundary becomes sufficient to activate slip of dislocations in the adjacent grain. This critical stress increases as the grain size decreases, and these physics are empirically captured by the Hall-Petch relationship,
:
where
is the yield stress,
is a material-specific constant that accounts for the effects of all other strengthening mechanisms,
is a material-specific constant that describes the magnitude of the metal’s response to grain size strengthening, and
is the average grain size. Additionally, because nanocrystalline grains are too small to contain a significant number of dislocations, nanocrystalline metals undergo negligible amounts of
strain-hardening,
and nanocrystalline materials can thus be assumed to behave with perfect plasticity.
As the grain size continues to decrease, a critical grain size is reached at which intergranular deformation, i.e. grain boundary sliding, becomes more energetically favorable than intragranular dislocation motion. Below this critical grain size, often referred to as the “reverse” or “inverse” Hall-Petch regime, any further decrease in the grain size weakens the material because an increase in grain boundary area results in increased grain boundary sliding. Chandross & Argibay modeled grain boundary sliding as viscous flow and related the yield strength of the material in this regime to material properties as
:
where
is the
enthalpy of fusion
In thermodynamics, the enthalpy of fusion of a substance, also known as (latent) heat of fusion, is the change in its enthalpy resulting from providing energy, typically heat, to a specific quantity of the substance to change its state from a s ...
,
is the atomic volume in the amorphous phase,
is the melting temperature, and
is the volume fraction of material in the grains vs the grain boundaries, given by
, where
is the grain boundary thickness and typically on the order of 1 nm. The maximum strength of a metal is given by the intersection of this line with the Hall-Petch relationship, which typically occurs around a grain size of
= 10 nm for BCC and FCC metals.
Due to the large amount of interfacial energy associated with a large volume fraction of grain boundaries, nanocrystalline metals are thermally unstable. In nanocrystalline samples of low-melting point metals (i.e.
aluminum
Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. It has ...
,
tin
Tin is a chemical element with the symbol Sn (from la, stannum) and atomic number 50. Tin is a silvery-coloured metal.
Tin is soft enough to be cut with little force and a bar of tin can be bent by hand with little effort. When bent, t ...
, and
lead
Lead is a chemical element with the symbol Pb (from the Latin ) and atomic number 82. It is a heavy metal that is denser than most common materials. Lead is soft and malleable, and also has a relatively low melting point. When freshly cut, l ...
), the grain size of the samples was observed to double from 10 to 20 nm after 24 hours of exposure to ambient temperatures.
Although materials with higher melting points are more stable at room temperatures, consolidating nanocrystalline feedstock into a macroscopic component often requires exposing the material to elevated temperatures for extended periods of time, which will result in coarsening of the nanocrystalline microstructure. Thus, thermally
stable nanocrystalline alloys are of considerable engineering interest. Experiments have shown that traditional microstructural stabilization techniques such as grain boundary pinning via solute segregation or increasing solute concentrations have proven successful in some alloy systems, such as Pd-Zr and Ni-W.
Nanocrystalline ceramics
While the mechanical behavior of ceramics is often dominated by flaws, i.e. porosity, instead of grain size, grain-size strengthening is also observed in high-density ceramic specimens.
Additionally, nanocrystalline ceramics have been shown to sinter more rapidly than bulk ceramics, leading to higher densities and improved mechanical properties,
although extended exposure to the high pressures and elevated temperatures required to sinter the part to full density can result in coarsening of the nanostructure.
The large volume fraction of grain boundaries associated with nanocrystalline materials causes interesting behavior in ceramic systems, such as
superplasticity
In materials science, superplasticity is a state in which solid crystalline material is deformed well beyond its usual breaking point, usually over about 600% during tensile deformation. Such a state is usually achieved at high homologous temp ...
in otherwise brittle ceramics. The large volume fraction of grain boundaries allows for a significant diffusional flow of atoms via
Coble creep, analogous to the grain boundary sliding deformation mechanism in nanocrystalline metals. Because the diffusional creep rate scales as
and linearly with the grain boundary diffusivity, refining the grain size from 10 μm to 10 nm can increase the diffusional creep rate by approximately 11 orders of magnitude. This superplasticity could prove invaluable for the processing of ceramic components, as the material may be converted back into a conventional, coarse-grained material via additional thermal treatment after forming.
Processing
While the synthesis of nanocrystalline feedstocks in the form of foils, powders, and wires is relatively straightforward, the tendency of nanocrystalline feedstocks to coarsen upon extended exposure to elevated temperatures means that low-temperature and rapid densification techniques are necessary to consolidate these feedstocks into bulk components. A variety of techniques show potential in this respect, such as
spark plasma sintering Spark plasma sintering (SPS), also known as field assisted sintering technique (FAST) or pulsed electric current sintering (PECS), or plasma pressure compaction (P2C) is a sintering technique.
The main characteristic of SPS is that the pulsed or u ...
or
ultrasonic additive manufacturing,
although the synthesis of bulk nanocrystalline components on a commercial scale remains untenable.
See also
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Nanocrystal
*
Nanoparticle
A nanoparticle or ultrafine particle is usually defined as a particle of matter that is between 1 and 100 nanometres (nm) in diameter. The term is sometimes used for larger particles, up to 500 nm, or fibers and tubes that are less than 1 ...
*
Quantum dot
Quantum dots (QDs) are semiconductor particles a few nanometres in size, having optical and electronic properties that differ from those of larger particles as a result of quantum mechanics. They are a central topic in nanotechnology. When the ...
References
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Crystals
Nanomaterials
Metallurgy